CN101190792A - Method for synthesizing titanium-silicon molecular screen - Google Patents
Method for synthesizing titanium-silicon molecular screen Download PDFInfo
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Abstract
A method of synthesizing titanium silicate molecular sieve is to hydrothermally crystallize the hydrolytic solution of silicon and titanium in a closed reaction vessel and then recycle the product. The method is characterized in that the hydrolytic solution of silicon and titanium is gotten by any one of the following three methods: A. under ultrasonic agitation, silicon source is first hydrolyzed in organo-alkali compound solution and then the titanium source is hydrolyzed in the solution; B. under the ultrasonic agitation, titanium source is first hydrolyzed in organo-alkali compound solution and then the silicon source is hydrolyzed in the solution; C. under the ultrasonic agitation, silicon source and titanium source are respectively hydrolyzed in organo-alkali compound solution and then mixed together. The synthetic method can eliminate partial uneven concentration, leads the amount of TiO2 generated by self agglomeration after the hydrolysis of titanium source to be as little as possible and reduces the production of extra framework titanium. Compared with the prior art, the TS-1 molecular sieve synthesized by the method not only has better catalytic oxidation activity and selectivity but also has better stability of catalytic activity.
Description
Technical field
The present invention relates to a kind of method of synthesis of titanium silicon molecular sieve, more specifically to synthetic method with HTS (TS-1) of MFI structure.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.Wherein the TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve is in organic oxidizing reaction, can adopt free of contamination lower concentration hydrogen peroxide as oxygenant, oxidising process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction preference, therefore have great prospects for commercial application.
The synthetic method of TS-1 disclosed (GB 2071071A, USP 4410501) first by people such as gondola Marco Taramasso in 1981.This method is earlier synthetic a kind of silicon source, titanium source, organic bases (RN of containing
+) and/or basic oxide (Me
N/2O) reaction mixture, with this reaction mixture in autoclave in 130-200 ℃ of hydrothermal crystallizing 6-30 days, separate then, wash, dry, roasting and product.In becoming the glue process, the mixing solutions hydrolysising condition of estersil and titanium ester is very harsh, because the hydrolysis rate of the two does not match, the latter is higher than the former, and the speed that adds organic bases will produce the polymer of irreversible titanium slightly soon, and the polymer of these titaniums is difficult to enter skeleton in crystallization process, and be entrained in the middle of the molecular sieve with the form of extra-framework titanium, this part titanium both may stop up the duct, again can the catalytic decomposition hydrogen peroxide, and the waste starting material.
People such as Thangaraj think enter skeleton in the TS-1 molecular sieve that aforesaid method synthesizes effective titanium content seldom, so they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of titanium content in the skeleton in 1992,1992, Vol.12:943), it is said that the Si/Ti of the method gained molecular sieve that people such as Taramasso can be proposed is than dropping to 20 from 39.Promptly prior art has been done the improvement of three aspects: the one, adopting the slower butyl (tetra) titanate of hydrolysis rate is the titanium source, the 2nd, the titanium source is dissolved in the anhydrous isopropyl alcohol, the 3rd, adjust order of addition(of ingredients), the aqueous isopropanol in titanium source is joined in the estersil solution of hydrolysis.In the technology of existing synthesis of titanium silicon molecular sieve (as Zeolites, 1992, Vol.12:943) in, though the content that adopting improves one's methods can make the skeleton titanium improves, but fundamentally do not solve into the aggregation problem of titanium in the glue process, Same Way of different experiments chamber employing so far synthetic TS-1 of institute difference in quality is big just for this, even the performance of the synthetic different batches of same operator is also unstable, the major cause of poor repeatability.
Under the ultrasonic wave radiation, produce the collapse moment of countless small cavity bubbles in the medium, can emit great energy and huge pressure, promptly in medium, produce a series of extreme conditions that approach, as the high temperature of moment, high pressure etc., these energy have played light, electricity, the by the use of thermal means effect of being beyond one's reach in material is synthetic.Ultransonic cavatition is seen uniform mixing with the synthetic technology that the stirring of machinery is merged mutually with desired Jie of the narrow distribution nano-powder of easier realization particle, eliminates the partial concn inequality, can also play shearing action to coacervate simultaneously.In recent years; ultrasonic technology is as a kind of novel synthetic technology; being subjected to people just day by day pays close attention to; it has demonstrated great potential at chemistry and material aspect synthetic; for example; the report of the nano material of being applied on synthetic arranged, and (the big woods of state etc., " SCI " in August, 2002, the 1592-1594 page or leaf is used for synthesis of nano TiO
2Ren Zhen etc., " chemical industry journal " in January, 2006, the 210-213 page or leaf is used for synthesis of nano SiO
2Deng), have to be applied in the report (Wu Jianmei etc., " catalysis journal " in May, 2006,375-377 page or leaf) that the MCM-49 Si-Al molecular sieve synthesizes; The report (intercalation bright great waves etc., " Chinese Journal of Inorganic Chemistry " in February, 2004,219-224 page or leaf) that is applied in synthetic pure silicon mesopore molecular sieve is arranged.
Summary of the invention
In the process of synthetic TS-1 HTS, be with pure silicon molecular sieve or Si-Al molecular sieve difference, prevent the polymerization of titanium in becoming the glue process, prevent that promptly titanium is derived from the irreversible TiO of generation that reunites
2Be crucial.
Also do not find up to now ultrasonic technique be used for HTS, especially for the report of synthetic TS-1 molecular sieve.The inventor finds through a large amount of compound experiments, ultrasonic technique is introduced in the building-up process of TS-1, and the minimizing titaniums are derived to reunite and generate irreversible TiO in a large number
2, reduce the generation of extra-framework titanium.
Therefore, the objective of the invention is on the basis of existing technology, a kind of polymerization of titanium in becoming the glue process that prevent is provided, reduce the method for the synthesis of titanium silicon molecular sieve (TS-1) of extra-framework titanium generation.
TS-1 molecular sieve synthetic method provided by the invention, be with the hydrating solution hydrothermal crystallizing of silicon, titanium in closed reactor, and recovery product, the hydrating solution that it is characterized in that said silicon, titanium is to obtain with in following described three kinds of modes any one: A, under ultrasonic agitation after the hydrolysis makes the silicon source hydrolysis of titanium source in wherein earlier in the organo-alkali compound aqueous solution again; B, under ultrasonic agitation, earlier the titanium source is made again the hydrolysis of silicon source in wherein in the organo-alkali compound aqueous solution after the hydrolysis; C, under ultrasonic agitation, with silicon source and titanium source respectively in the organo-alkali compound aqueous solution hydrolysis again row mix.
In the method provided by the invention, the hydrating solution of said silicon titanium, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.001-0.5): (0.001-0.80): (5-100), preferred 1: (0.005-0.5): (0.05-0.5): (10-100), wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
In the method provided by the invention, said ultrasonic agitation is meant utilizes ultrasonic wave and mechanical stirring to make it mixing, promptly utilizes synthetic technology that ultransonic cavatition and mechanical stirring merge mutually to make it the technology of mixing.
In the method provided by the invention, said silicon source is silica gel, silicon sol or organosilicon acid esters, wherein preferred organic silicon ester.Its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1Be preferably alkyl, be more preferably ethyl with 1-4 carbon atom.
In the method provided by the invention, said titanium source is inorganic titanium salt or organic titanate, wherein preferably has organic titanate.Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
2)
4, R wherein
2For having the alkyl of 1-6 carbon atom, preferably has the alkyl of 2-4 carbon atom.
In the method provided by the invention, said organo-alkali compound is a TPAOH, perhaps the mixture formed of TPAOH and fat amine compound or alcamine compound.
Its general formula of said fat amine compound is R
3(NH
2)
n, R wherein
3Be alkyl or alkylidene group with 1-4 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
Its general formula of said alcamine compound is (HOR
4)
mNH
(3-m)R wherein
4For having the alkyl of 1-4 carbon atom, m=1,2 or 3, wherein preferred alcamine compound is monoethanolamine, diethanolamine or trolamine.
In the method provided by the invention, said hydrothermal crystallization process is known by those of ordinary skill in the art, normally mixture is handled 2-360 hour, preferred 10-240 hour under 80-200 ℃, preferred 80-180 ℃ of autogenous pressure in sealed reactor.
The method of synthesis of titanium silicon molecular sieve provided by the invention (TS-1) has following advantage:
1, utilize the ultrasonic agitation technology to eliminate partial concn inequality in the building-up process, the TiO that makes the titanium source reunite and generate
2Few as far as possible, reduce the generation of extra-framework titanium.
2, because ultrasonic agitation impels silicon source and titanium source to combine with the organic bases template is better, make organic bases better play the effect of template, reduced expensive organic bases template agent, reduced synthetic cost; Crystal nucleation speed has been accelerated in ultrasonication, has accelerated resultant velocity.
3, its catalytic oxidation activity of product and the selectivity of utilizing the ultrasonic agitation technology to synthesize compared with prior art obviously improves, and has stability of catalytic activity preferably simultaneously, for example brings up to more than 86% by 72% at product yield.
4, the ultrasonic agitation technology is simple and easy to operate, and it is good to repeat preparation property, and the sample homogeneity is good.
Description of drawings
Fig. 1 (A) be Comparative Examples 1 by prior art (Zeolites, 1992, Vol.12:943) X-ray diffraction (XRD) the crystalline phase figure of Zhi Bei TS-1 sieve sample.
Fig. 1 (B) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
Fig. 1 (C) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 2 gained samples.
Fig. 2 (a) be Comparative Examples 1 by prior art (Zeolites, 1992, Vol.12:943) fourier infrared (FT-IR) spectrogram of preparation gained TS-1 sieve sample.
Fig. 2 (b) is fourier infrared (FT-IR) spectrogram of embodiment 1 gained sample.
Fig. 2 (c) is fourier infrared (FT-IR) spectrogram of embodiment 2 gained samples.
Embodiment
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.Used reagent is commercially available chemically pure reagent among Comparative Examples and the embodiment.Used ultrasonic wave is KQ-100DE type numerical control supersonic cleanser (220 volts of operating voltage, 50 hertz that Kunshan Ultrasonic Instruments Co., Ltd. produces; 40 kilo hertzs of operating frequencies; 100 watts of ultrasonic electric power).X-ray diffraction (XRD) the crystalline phase figure that carries out sample on Siemens D5005 type x-ray diffractometer measures, and gamma ray source is CuK α (λ=1.5418
), tube voltage 40kV, tube current 40mA, 0.5 °/min of sweep velocity, sweep limit 2 θ=4 °-40 °.The fourier infrared of sample (FT-IR) spectrogram is measured on Nicolet 8210 type Fourier infrared spectrographs, adopts KBr compressing tablet (sample accounts for 1wt%), test specification 500-1500cm under the vacuum
-1
Comparative Examples 1
This Comparative Examples is for pressing prior art Zeolites, 1992, the TS-1 sieve sample of the method preparation described in the Vol.12 943-950 page or leaf, being about to the positive tetraethyl orthosilicate of 22.5 grams mixes with 7.0 gram TPAOH, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add the solution of forming by 1.1 gram tetrabutyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, the gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, washes with water, and, obtain the former powder of TS-1 in 110 ℃ of dryings 60 minutes.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, the TS-1 molecular sieve.Yield is about 72%, and (quality that is the TS-1 molecular sieve that obtains after the roasting accounts for the silicon source of input (with SiO
2The meter) and the titanium source (with TiO
2The per-cent of total mass meter)).Its XRD crystalline phase figure is shown in Fig. 1 (A), and the fourier infrared spectrogram is shown in Fig. 2 (a).
Embodiment 1
Positive tetraethyl orthosilicate and tetrabutyl titanate are joined successively ultrasonic agitation mixes in the aqueous solution of TPAOH, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and water is 1: 0.04: 0.05: 25, obtained titanium, silicon hydrating solution in 2 hours at normal pressure and 40 ℃ of following hydrolysis.This titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 24 hours under 170 ℃ temperature and autogenous pressure, and the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 90%.Its XRD crystalline phase figure is shown in Fig. 1 (B), and is similar with Comparative Examples; The fourier infrared spectrogram is shown in Fig. 2 (b), and is also similar with Comparative Examples, at 960cm
-1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has entered framework of molecular sieve.
Tetrabutyl titanate and positive tetraethyl orthosilicate successively being joined in the aqueous solution of TPAOH ultrasonic agitation mixes and obtains titanium, silicon hydrating solution, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and water is 1: 0.1: 0.15: 55, this titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 72 hours under 150 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 89%.Its XRD crystalline phase figure is shown in Fig. 1 (C), and is similar with Comparative Examples; The fourier infrared spectrogram is shown in Fig. 2 (c), and is similar with Comparative Examples, in the infrared spectrum at 960cm
-1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has entered framework of molecular sieve.
Embodiment 3
Positive tetraethyl orthosilicate and tetrabutyl titanate being joined in the aqueous solution of TPAOH and trolamine ultrasonic agitation respectively mixes back remix ultrasonic agitation for some time and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, the mol ratio of trolamine and water is 1: 0.2: 0.15: 0.15: 85, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 96 hours under 130 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 88%, is the TS-1 molecular sieve through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample.
Embodiment 4
Positive tetraethyl orthosilicate and tetraethyl titanate successively being joined in the aqueous solution of TPAOH ultrasonic agitation mixes and obtains titanium, silicon hydrating solution, the mol ratio of wherein positive tetraethyl orthosilicate, tetraethyl titanate, TPAOH and water is 1: 0.05: 0.35: 45, this titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 72 hours under 110 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 89%, is the TS-1 molecular sieve through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample.
Positive tetraethyl orthosilicate and tetrabutyl titanate successively being joined in the aqueous solution of TPAOH and quadrol ultrasonic agitation mixes and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, the mol ratio of quadrol and water is 1: 0.2: 0.25: 0.4: 75, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 48 hours under 180 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 86%, is the TS-1 molecular sieve through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample.
Embodiment 6
Positive tetraethyl orthosilicate and tetraethyl titanate successively being joined in the aqueous solution of TPAOH ultrasonic agitation mixes and obtains titanium, silicon hydrating solution, the mol ratio of wherein positive tetraethyl orthosilicate, tetraethyl titanate, TPAOH and water is 1: 0.05: 0.35: 95, this titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 96 hours under 140 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 87%, is the TS-1 molecular sieve through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample.
Embodiment 7
Positive tetraethyl orthosilicate and tetraethyl titanate successively being joined in the aqueous solution of TPAOH and trolamine ultrasonic agitation mixes and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetraethyl titanate, TPAOH, the mol ratio of trolamine and water is 1: 0.05: 0.25: 0.35: 55, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 48 hours under 170 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ roasting temperature 3 hours, obtain the TS-1 molecular sieve then.Yield is about 86%, is the TS-1 molecular sieve through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample.
Embodiment 8
The method gained sample of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
The sample that the foregoing description and Comparative Examples is prepared is according to sample: phenol: the weight ratio of acetone=1: 20.0: 16.0 mixes in a there-necked flask that has a prolong, be warming up to 80 ℃, then under whipped state according to phenol: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 27.5 heavy %, reaction is 3 hours under this temperature, products therefrom uses the OV-101 capillary column on the Varian3400 chromatographic instrument (30m * 0.25mm) measure each product to distribute the results are shown in Table 1.In table 1:
Table 1
From table 1 we as can be seen: the phenol hydroxylation activity of gained sample of the present invention is apparently higher than comparative sample, and selectivity also increases to some extent, and its catalytic oxidation activity of sample and the compared with prior art obviously raising of selectivity of preparation method's gained of the present invention be describeds.
Embodiment 9
The method gained TS-1 molecular sieve of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of ammoxidation of cyclohexanone.With the TS-1 molecular sieve of gained among the embodiment 1 according to TS-1: the trimethyl carbinol: the weight ratio of 25 heavy % ammoniacal liquor=1: 7.5: 7.5 mixes in slurry bed, be warming up to 80 ℃ and under whipped state, add the mixture (volume ratio of water and hydrogen peroxide is 10: 9) of the hydrogen peroxide of entry and 30 heavy % with 5.7 milliliters/hour speed, the mixture (volume ratio of the pimelinketone and the trimethyl carbinol is 1: 2.5) that adds the pimelinketone and the trimethyl carbinol with 10.5 milliliters/hour speed, adding the quality percentage composition with 5.7 milliliters/hour speed is 25% ammoniacal liquor, above-mentioned three bursts of streams are for adding simultaneously, simultaneously with the continuous discharging of corresponding speed, every 2 hours product sampling is analyzed with chromatogram after the stable reaction, the production rate of cyclohexanone-oxime is defined as follows, and gained the results are shown in Table 2.
Table 2
| First day average | Second day average | The 3rd day average | The 4th day average | |
| The production rate % of cyclohexanone-oxime | 81.46 | 84.58 | 87.94 | 87.05 |
The TS-1 molecular sieve through roasting of Comparative Examples 1 gained is carried out the ammoxidation of cyclohexanone reaction evaluating by above-mentioned identical method, every 1 hour product is carried out sampling analysis, the results are shown in Table 3 for gained.
Table 3
| The 2nd hour | The 6th hour | The 10th hour | |
| The production rate % of cyclohexanone-oxime | 58.72 | 38.46 | 31.95 |
Comparing result by table 2 and table 3 shows that the inventive method gained TS-1 molecular sieve has catalytic activity and activity stability preferably.
Claims (14)
1. the method for a synthesis of titanium silicon molecular sieve, be with the hydrating solution hydrothermal crystallizing of silicon, titanium in closed reactor, and recovery product, the hydrating solution that it is characterized in that said silicon, titanium is to obtain with in following described three kinds of modes any one: A, under ultrasonic agitation after the hydrolysis makes the silicon source hydrolysis of titanium source in wherein earlier in the organo-alkali compound aqueous solution again; B, under ultrasonic agitation, earlier the titanium source is made again the hydrolysis of silicon source in wherein in the organo-alkali compound aqueous solution after the hydrolysis; C, under ultrasonic agitation, with silicon source and titanium source respectively in the organo-alkali compound aqueous solution hydrolysis again row mix.
2. according to the method for claim 1, it is characterized in that the hydrating solution of said silicon, titanium, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.001-0.5): (0.001-0.80): (5-100); Wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
3. according to the method for claim 1 or 2, wherein said silicon source is silica gel, silicon sol or organosilicon acid esters.
4. according to the method for claim 3, wherein said organosilicon acid esters, its general formula are R
1 4SiO
4, R
1Be selected from alkyl with 1-4 carbon atom.
5. according to the method for claim 1 or 2, wherein said titanium source is inorganic titanium salt or organic titanate.
6. according to the method for claim 5, wherein said inorganic titanium salt is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
7. according to the method for claim 5, wherein said its general formula of organic titanate is Ti (OR
2)
4, R
2Be selected from alkyl with 1-6 carbon atom.
8. according to the method for claim 7, wherein said R
2Be selected from alkyl with 2-4 carbon atom.
9. according to the method for claim 2, the hydrating solution of wherein said titanium, silicon, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.005-0.5): (0.05-0.5): (10-100).
10. according to the method for claim 1 or 2, wherein said organo-alkali compound is a TPAOH, or is the mixture that TPAOH and fat amine compound or alcamine compound are formed.
11. according to the method for claim 10, wherein said its general formula of fat amine compound is R
3(NH
2)
n, R
3Be selected from alkyl or alkylidene group, n=1 or 2 with 1-4 carbon atom.
12. according to the method for claim 11, wherein said fat amine compound is selected from ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
13. according to the method for claim 10, wherein said its general formula of alcamine compound is (HOR
4)
mNH
(3-m), R
4Be selected from alkyl, m=1,2 or 3 with 1-4 carbon atom.
14. according to the method for claim 13, wherein said alcamine compound is monoethanolamine, diethanolamine or trolamine.
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| CN102372280A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve with mobil five (MFI) structure and preparation method thereof |
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| US9486790B2 (en) | 2011-10-31 | 2016-11-08 | Dalian University Of Technology | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
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| CN102614911B (en) * | 2012-02-23 | 2014-08-06 | 湘潭大学 | One-step molding method of titanium silicalite molecular sieve |
| CN103769068B (en) * | 2012-10-25 | 2016-04-06 | 中国石油化工股份有限公司 | Ti-base catalyst and preparation method thereof |
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| CN104512904A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Mesoporous titanium-silicon material preparation method |
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| CN104030312A (en) * | 2014-05-09 | 2014-09-10 | 神马实业股份有限公司 | Synthetic method for titanium-silicon molecular sieve TS-1 |
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| CN104692408A (en) * | 2015-02-13 | 2015-06-10 | 南京航空航天大学 | Method for preparing propylene epoxide through propylene cyclization under catalysis of molybdenum/titanium silicalite molecular sieve |
| CN106006665A (en) * | 2016-05-13 | 2016-10-12 | 浙江师范大学 | Method for preparing titanium silicalite molecular sieve TS-1 |
| CN106006665B (en) * | 2016-05-13 | 2018-08-21 | 浙江师范大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| CN111253449B (en) * | 2018-11-30 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing fructose |
| CN111253449A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing fructose |
| CN111905798B (en) * | 2019-05-09 | 2023-04-07 | 中国科学院大连化学物理研究所 | Preparation method and application of titanium-containing mesoporous material MCM-41 |
| CN111905798A (en) * | 2019-05-09 | 2020-11-10 | 中国科学院大连化学物理研究所 | Preparation method and application of titanium-containing mesoporous material MCM-41 |
| CN112570021A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Nano material and preparation method thereof |
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| CN116173723A (en) * | 2021-11-26 | 2023-05-30 | 中国石油化工股份有限公司 | VOCs gas oxidation method |
| CN116173723B (en) * | 2021-11-26 | 2024-10-11 | 中国石油化工股份有限公司 | VOCs gas oxidation method |
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